基于石墨烯载体的铁基材料制备及除砷性能比较

以氧化石墨为前驱体,分别将磁铁矿、赤铁矿和零价铁负载到石墨烯上,通过FTIR和XRD对其进行表征,成功地制备出石墨烯负载磁铁矿(M-RGO)、石墨烯负载赤铁矿(H-RGO)和石墨烯负载零价铁(N-RGO)这3种复合材料.研究比较了3种复合材料的除砷性能,如吸附动力曲线、吸附等温线、pH值范围和共存离子对除砷效果影响.结果表明,3种材料吸附As(Ⅲ)的动力曲线遵从准二级动力学模型,吸附等温线符合Langmuir模型,在相同条件下,其吸附容量依次为N-RGO>MRGO>H-RGO.3种材料均在弱酸性至中性条件下对As(Ⅲ)有较好的吸附效果,M-RGO和H-RGO材料受pH值影响较小,且吸附As(Ⅲ)的最佳pH值范围较N-RGO材料宽.3种材料中,N-RGO材料抗共存离子干扰能力较强,其次是H-RGO材料,MRGO材料最差.     

磁性CeO_2-Fe_3O_4复合材料光催化/吸附去除水中As(Ⅲ)

原水砷污染问题严重威胁饮用水水质安全,随着生活饮用水标准的提高,致使多地饮用水中砷超标问题突显.本研究利用CeO_2半导体的光催化活性及CeO_2和Fe_3O_4对As(Ⅴ)的强亲和力,合成了双组份磁性CeO_2-Fe_3O_4复合材料,并采用SEM、XRD、BET和VSM等手段进行表征,考察复合材料的光催化/吸附除砷效果;研究了初始p H值、共存离子等因素对吸附除砷效果的影响;采用等温吸附模型、吸附动力学模型等手段进行吸附特性研究.实验结果表明,在光催化过程中,·OH和·O_2~-为主要的活性氧化物种.在紫外照射下,As(Ⅲ)能完全被氧化为毒性较低的As(Ⅴ),同时将As(Ⅴ)高效吸附于CeO_2-Fe_3O_4粒子表面.在中性条件下,CeO_2-Fe_3O_4粒子对砷的饱和吸附量为122.19 mg·g~(-1).共存离子Cl~-和SO_4~(2-)对As(Ⅴ)的吸附没有显著影响,而CO_3~(2-)、SiO_3~(2-)和PO_4~(3-)与As(Ⅴ)存在明显的竞争吸附,使As(Ⅴ)的吸附去除效果明显降低.吸附动力学和吸附等温线模拟分别符合准二级动力学方程和Freundlich吸附等温线,表明As(Ⅴ)的吸附以化学吸附为主导.CeO_2-Fe_3O_4复合吸附剂可快速实现固液分离,容易再生且重复利用性较好,具有广泛的应用前景.     

新型铁铜锰复合氧化物颗粒吸附剂As(Ⅲ)吸附行为与机制研究

以壳聚糖为黏合剂,采用包覆法制备了一种新型除砷吸附剂——颗粒状铁铜锰复合氧化物(GFCM). GFCM吸附剂为不完全球状,直径0.7～1.0 mm,可以有效地将As(Ⅲ)氧化成As(V),并对形成的As(V)具有良好的吸附效果. GFCM对As(Ⅲ)的最大吸附容量(pH 7.0)为56.5 mg·g~(-1),显著优于目前已报道的多数颗粒状除砷吸附剂.溶液pH在5.0～9.0范围内, GFCM对As(Ⅲ)均有较好的吸附效果,离子强度则对砷吸附效果影响较小.共存阴离子对As(Ⅲ)吸附具有抑制作用,影响的大小顺序为:PO■ SiO■ CO■ Cl~- SO■.吸附As(Ⅲ)后的GFCM可用NaOH溶液进行有效脱附再生,可重复使用.在As(Ⅲ)的去除过程中,吸附剂中锰氧化物的主要作用是氧化As(Ⅲ),铁氧化物与铜氧化物的主要作用是吸附As(Ⅲ)与氧化形成的As(V),且铜氧化物有助于增强GFCM的砷吸附性能.     

赤铁矿对砷的吸附解吸及氧化特征

采用等温吸附热力学的方法,研究了赤铁矿(α-Fe2O3)对三价砷离子的吸附和氧化特征,以及温度、pH值等因素对吸附和氧化效果的影响.研究结果表明,Langmuir方程可以很好地表述吸附量与初始三价砷离子浓度的关系(R2=0.9939);随着初始砷离子浓度的增大,溶液中As(V)的浓度(氧化量)也逐渐增大,然而氧化率却随着初始砷离子浓度的增大而减小;35℃条件下的吸附量和吸附率、氧化量和氧化率都比25℃时大,表明升高温度有利于赤铁矿对砷离子的吸附和氧化作用.溶液酸度对于As(Ⅲ)的吸附和氧化有着不同的影响,在pH<8时,吸附量和吸附率随pH上升而增加,在pH=8时达到最大,随后随pH上升而减小;当pH低于6.0时,随着pH的增加As(Ⅲ)氧化量、氧化率逐渐增大,而当pH高于6.0时.随着pH增加As(Ⅲ)氧化量反而降低.最大氧化量出现在pH=6.0处.     

Fe@GOCS的制备及其对水中As(Ⅲ)的吸附

基于自组装原理混合了氧化石墨烯、壳聚糖和FeCl_3·6H_2O,并使用NaOH溶液固定,戊二醛-甲醇溶液交联后得到了不同载铁量的载铁氧化石墨烯壳聚糖(Fe@GOCS)球形材料,采用静态吸附实验研究其对水溶液中As(Ⅲ)的吸附去除及机制.结果表明,吸附剂负载的铁以α-FeO(OH)形态为主,对As(Ⅲ)的吸附容量随pH的降低呈上升趋势,实验最佳pH值为3.在温度298.15、 308.15和318.15 K且pH值为3条件下,As(Ⅲ)的吸附反应在45 h左右达到平衡,吸附剂最佳投加量为1.0 g·L~(-1),最大吸附容量可达289.4mg·g~(-1). 5次吸附-解吸附后,吸附容量未下降,反而呈上升趋势.热力学结果显示:ΔG~θ0、ΔS~θ0和ΔH~θ0,表明Fe@GOCS对As(Ⅲ)的吸附过程是吸热和熵增的自发反应,升温利于吸附;吸附过程符合伪二级动力学方程,Freundlich和Sips等温吸附模型能更好地描述对As(Ⅲ)的吸附行为.结合材料表征测试结果,认为离子交换和表面络合是Fe@GOCS去除As(Ⅲ)的主要机制.     

磁性海藻酸铁介孔碳微球的合成及对水体中砷的去除

本研究以海藻酸钠作为基体前驱材料,利用离子交联法合成了海藻酸铁微球,然后进一步运用真空冷冻和高温裂解法制备了表面附着纳米铁氧化物的磁性海藻酸铁介孔碳微球(MAMC).同时,采用热场发射扫描电镜显微镜、X射线光电子能谱、热重分析仪、磁学测量系统、BET比表面孔径分析仪等对MAMC进行表征,并研究了MAMC对As(Ⅲ)和As(Ⅴ)的吸附性能,重点考察投加量、pH、时间、初始污染物浓度对吸附性能的影响,并对吸附过程进行了动力学拟合和等温吸附方程拟合,最后对材料进行了再生实验.结果表明,MAMC对As(Ⅲ)和As(Ⅴ)均表现出良好的吸附性能,对As(Ⅲ)的吸附能力优于As(Ⅴ);当pH值为5~7时,MAMC对两种价态As的吸附效率最优;材料的吸附量随着时间的增加而增加.动力学拟合结果表明,MAMC的吸附过程较好地满足准二级动力学方程,等温吸附曲线较好地满足于Langmuir方程.此外,使用0.1 mol·L~(-1)的Na OH对材料的再生和脱附效果较好,能够实现材料的二次利用.本研究结果对处理含砷废水提供了重要的理论依据.     

砷氧化菌对胡敏酸络合As (Ⅲ)的氧化作用

土壤砷与土壤微生物相互作用是土壤砷形态转化中需要重点关注的内容之一.为了研究砷氧化菌对胡敏酸络合三价砷[HA-As(Ⅲ)]的作用,设置了不同p H值反应体系,研究砷氧化菌HN-2对HA-As(Ⅲ)作用下,砷的形态变化及其在固液两相中的分配.结果表明,在HA与As(Ⅲ)络合过程中,HA可以将一部分游离态As(Ⅲ)氧化为As(Ⅴ).其中,在p H=7的体系中,As(Ⅲ)被HN-2和HA氧化成As(Ⅴ)的效率最高.在含有砷氧化菌株和不含砷氧化菌株的体系中,0~10 h振荡过程中,HA-As材料均可以释放一部分As(Ⅲ)及As(Ⅴ)进入液相中,同时砷氧化菌可以快速地将As(Ⅲ)氧化为As(Ⅴ),而胡敏酸可以较缓慢地将As(Ⅲ)氧化为As(Ⅴ);反应10~24 h期间,HN-2砷氧化菌可以将络合态HA-As(Ⅲ)转化为游离态As(Ⅲ)并氧化为As(Ⅴ);48 h后反应逐渐达到平衡.固相同步辐射结果可以进一步证明HN-2砷氧化菌对络合态As(Ⅲ)的释放及氧化作用.     

新型离子印迹材料的制备及吸附重金属应用进展

离子印迹技术用于选择性吸附废水中痕量金属资源备受关注,采用新型材料组分制备离子印迹材料的研究取得了良好效果。文章以废水中金属资源提取及有毒金属去除为目的,简述了传统本体聚合法、悬浮聚合法、凝胶-溶胶法、表面接枝法的优缺点,阐述了天然矿物基、天然生物基、成品膜及混合铸膜基、温敏聚合层基、磁性硅基、磁性碳纳米管基、磁性氧化石墨烯基的制备应用进展;探讨了新型离子印迹复合材料的优势,最后指出离子印迹材料在自然水体、工业废水的应用及回收问题并提出建议,期望为制备新型离子印迹材料对复杂水相选择吸附应用研究提供参考。     

磁性吸附材料CuFe2O4吸附砷的性能

根据Cu(Ⅱ)和Fe(Ⅲ)都对砷有较强的亲和性,制备了同时含有Cu(Ⅱ)和Fe(Ⅲ)的、可用磁分离方法进行分离回收的磁性吸附材料CuFe₂O₄,并对其进行了表征及吸附砷的性能研究.结果表明,该吸附剂对砷的吸附能力与溶液pH有关,在弱酸性及中性条件下,吸附砷的能力最强,而对As(V)的吸附能力比对As(Ⅲ)更强些,在平衡浓度为10μg/L时,其吸附容量可达10mg/g左右,可以很容易地将水中浓度为1～20mg/L的As(V)降到10μg/L以下.实验考察了几种无机阴离子对吸附砷的影响,表明较高浓度(砷浓度的20倍)的硫酸盐对As(Ⅲ)和As(V)的吸附均有一定影响,盐酸盐及磷酸盐则影响不明显;负载的As(V)可较容易地用0.1mol/L NaOH洗脱下来,使吸附剂再生,而As(Ⅲ)则难以洗脱,这与2种价态砷的吸附机理不同有关.     

几种吸附材料对水中砷(Ⅲ)去除效果比较

As(Ⅲ)是一种高毒性的化学物质,对人体具有致癌作用。研究调查了实验室合成的纳米铁和其它几种价格低廉的吸附剂对水中As(Ⅲ)的去除效率。通过批实验对八种不同吸附材料进行了比较:自制纳米铁(ZZ-NZVI),尊业纳米铁(ZY-NZVI),活性炭(AC),铸铁屑(CSI),膨润土(B),石墨化碳黑(GCB),纳米碳(NC)和红砖(RB)。这些吸附材料对As(Ⅲ)吸附动力学速率常数顺序依次为LS-NZVIZY-NZVICSI。反应1h时,0.25g纳米铁对起始质量浓度为910g/LAs(Ⅲ)的去除率高达99%以上,被处理后的水中As(Ⅲ)浓度低于10g/L.结果表明,具有高反应活性的纳米铁将成为饮用水中砷去除非常有效的吸附材料。     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.